Silver halide photographic colour material containing 1-(cyanoalkyl)-pyrazolone color couplers

ABSTRACT

PHOTOGRAPHIC LIGHT-SENSITIVE SILVER HALIDE ELEMENTS CONTAINING A NON-DIFFUSING 2-PYRAZOLIN-5-ONE COLOR COUPLER HAVING THE FORMULA   1-(CN-CH(-R2)-CH(-R1)-),3-R-PYRAZOLIN-5-ONE   WHEREIN R1 IS HYDROGEN, AN ALKYL GROUP OR AN ARYL GROUP AND R2 IS HYDROGEN OR AN ALKYL GROUP, AND R REPRESENTS AN ALKYL GROUP, AND ARYL GROUP, A HETEROCYCLIC GROUP, A -NH-ARYL GROUP, A-NH-CO-ALKYL GROUP, A-NHCOARYL GROUP, A-NH--NH-CO-ALKYL GROUP, A-NHCONHALKYL GROUP, A-NHCONH-ARYL GROU, A-NHCONHARALKYL GROUP, AN ALKOXYCARBONYLAMINO GROUP, AN ARYLOXYCARBONYLAMINO GROUP, OR AN ARALKYLOXYCARBONYLAMINO GROUP IS DESCRIBED. THESE PHOTOGRAPHIC ELEMENTS HAVE IMPROVED LIGHT STABILITY AND POSSESS FAVORABLE SPECTRAL AND SENSITOMERTIC PROPERTIES.

United States Patent 3,567,449 SILVER HALIDE PHOTOGRAPHIC COLOUR MATE- RIAL CONTAINING 1-(CYANOALKYL)-PYRAZO- LONE COLOR COUPLERS Hector Alfons Vanden Eynde, Mortsel, Robert Joseph Pollet, Berchem, and Arthur Henri De Cat, Mortsel, Belgium, assignors to Gevaert-Agfa N.V., Mortsel, Belgium No Drawing. Filed Aug. 31, 1967, Ser. No. 664,644 Claims priority, application Great Britain, Sept. 26, 1966, 42,823/66 Int. Cl. G03c 1/40 US. Cl. 96-565 4 Claims ABSTRACT OF THE DISCLOSURE Photographic light-sensitive silver halide elements containing a non-diffusing 2-pyrazolin-5-one color coupler having the formula H2C 1-( JR wherein R is hydrogen, an alkyl group or an aryl group and R is hydrogen or an alkyl group, and R represents an alkyl group, and aryl group, a heterocyclic group, a --NH-ary1 group, a NHCO-alkyl group, a -NHOO- aryl group, a -NH-CO-aralkyl group, aNHCONH- alkyl group, a NHCON'H-aryl group, a NI-I*CONH- aralkyl group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, or an aralkyloxycarbonylamino group is described. These photographic elements have improved light stability and possess favorable spectral and sensitometric properties.

This invention relates to 1-,8-cyanoalkyl-Z-pyrazolin-S- one colour couplers, to the preparation thereof, to photographic materials and developing compositions containing such colour couplers as well as to colour development processes wherein said colour couplers take part in the formation of a magenta dye image.

It is known that for the manufacture of a photographic colour image in a light-sensitive silver halide emulsion layer the exposed silver halide is developed to a silver image by means of an aromatic primary amino compound in the presence of a colour coupler, which by reaction with the oxidized developer forms a dye on the areas corresponding with the silver image.

In the subtractive three-colour photography usually a light-sensitive photographic colour material is used comprising a red-sensitized, a green-sensitized and a blue-sensitive silver halide emulsion layer wherein on development by means of suitable colour couplers, a cyan, a magenta and a yellow dye image are formed respectively.

According to the present invention 2-pyrazolin-5-one colour couplers are provided carrying in the 1-position a p-cyanoalkyl group corresponding to the formula:

NC-(fH-CH- R2 I ll wherein R represents an alkyl group or an aryl group and 'R stands for hydrogen or wherein R represents an "ice alkyl group and R stands for hydrogen. These colour couplers yield in the silver halide photographic process on colour development with aromatic primary amine developing agents azomethine dyes having an improved 5 light-stability and possessing favorable spectral and sensitometric properties.

By Z-pyrazolin-S-one compounds there is not only meant the simple 2-pyrazolin-5-one compounds but also the bis-Z-pyrazolin 5 one compounds the pyrazolinone nuclei of which are ioined in the 4-position by a bivalent radical (cf. Pierre Glafkides, Photographic Chemistry, vol. II, Fountain Press, London (1960) p. 602).

More particularly, according to the present invention colour couplers are provided corresponding to the general formula given below and bis-Z-pyrazolin-S-one compounds derived therefrom by linking the 2-pyrazolin-5- one nuclei in the 4-position by means of a bivalent radical.

alkyloxycarbonylamino group including these groups carrying further substituents.

The following is a non-limitative list of structural for mulae of colour couplers according to the present invention:

I S 03H an alkyl group, an aryl, group ora heterocyclic group can be prepared according to the method known by those skilled in the art by cyclisation of the appropriate B-cyanoalkylhydrazine with an acylacetic acid ester. 7

The 1- 3-cyanoalkyla2-pyrazolin-S-one colour ,couplers according to the present invention wherein R represents an arylamino group, an acylamino group, an ureido group, an alkoxycarbonylamino, an aryloxycarbonylamino group or an aralkyloxycarbonylamino group can be prepared, e.g., by application of one of the methods described in published Dutch patent application 65/ 13316, United Kingdom patent application Ser. No. 1,044,959, United Kingdom patent specification 1,007,847, and German patent application, (DAS) 1,176,479, starting from the corresponding 1pecyanOaIkyl-S-amino-2-pyrazolin-5 one compound. I W

The 1,-[3-cyanoalkyl-3-amino-2 pyrazolin 5 one .compounds used in said methods can be prepared according to the method known by those skilled in the art by cyclisation of an appropriate hydrazine with e.g. the ethyl ester of ,B-imino-/3-ethoxy-propionic acid.

T he bis-2-pyrazolin-5-one colour couplers joined in the 4-position by a bivalent radical can be prepared as is known, e.g., by allowing to react two molecules of a 2- pyrazolin-S-one according to the above general formula with one molecule of an aldehyde or ketone.

The following description illustrates the Preparation of colour couplers according to the present invention.

PREPARATION 1 1- (Z-cyanoethyl) -3 -octadecylureido-2-pyrazolin-5-one 1 (Formula 2) (a) g. of 2-cyanoethyl hydarzine, prepared according to H. Dorn et a1., Chem. Ber., 98, 3377 (1965), and 159.5 g. of B-ethoxy-B-imino-propionic acid ethyl ester are mixed in the presence of 1 g. of p-toluene-sulphonic acid. The temperature of the reaction mixture rises but is kept at 25-30 C. by cooling. After about 1 hour a product crystallizes, which is separated after having been kept standing overnight. The l-(i-cyanoethyl)-3-amin0- 2-pyrazolin-5-one is recrystallized from a mixture of ethanol and isopropylether (5:1). Melting point: 132.5 C.

(b) 15.2 g. of I-(Z-cyanoethyl)-3-amino-2-pyrazolin-5- one and 29.5 g. of octadecyl isocyanate are allowed to react at 75 C. in ml. of nitrobenzene in the presence of 26.7 g. of aluminium chloride (this method has been described in United Kingdom patent specification 1,007,- 847).

The reaction product is washed with water and meth anol and then recrystallized from ethanol. The product obtained melts at 157-159 C.

PREPARTION 2 1-(2-cyanoethyl)-3-(p-hexadecyloxybenzamido) -2- pyrazolin-S-one (Formula 4) 15.2 g. ,of 1-(Z-eyanoethyl)-3-amino-2-pyrazolin-5-one prepared as described in preparation 1(a) are allowed to react at 37 C. with 38 g. of p-hexadecyloxy-benzoylchloride in 100 ml. of nitrobenzene and the presence of 26.7 g. of aluminium chloride (this method has been described in United Kingdom patent specification 1,007,- 847 The reaction product is washed with water and warm methanol and then recrystallized from a mixture of ethylene glycol monomethyl ether and ethyl acetate. The white product obtained melts at 203 C.

PREPARATION 3 1- Z-cyahoethyl) -3 (2-hexadecyloxy-5-sulphobenzamido)-2-pyrazolin-5-one (Formula 6) 15.2 g. of 1-(2-cyanoethyl)-3-amino-2-pyrazolin-5-one prepared as described in Preparation 1(a) are allowed to react according to the method described in United States patent specification 2,829,975 with 44.2 g. of Z-hexadecyloxy-S-sulpho-benzoic acid (prepared analogously to the preparation of 3-sulpho-4-heXadecyloxy-benzoic acid as described in United Kingdom patent application Ser. No. 1,039,965) in the presence of 4.5 ml. of phosphorus trichloride and in a mixture of 80 ml. of pyridine and 160 ml. of benzene.

The reaction product is dissolved in 400 ml. of 2 N sodium hydroxide, filtered and acidified with hydrochloric acid. The precipitate formed is recrystallised from acetic acid.

The white product obtained does not melt-at a temperature lower than 200 C.

PREPARATION 4 1- (Z-cyanopropyl) -3 -(u-su1pho-stearoylamino) -2- pyrazolin-S-one (Formula 7) (a) 1-(2-cyanopropyl)-3-amino-2-pyrazolin 5 one is prepared analogously to the method of preparation 1(a) from 2-cyanopropyl hydrazine, which is a colourless liquid having a boiling point of 90 C./0.4 mm. and which is prepared analogously to 2-cyanoethyl hydrazine according to H. Dorn et al., Chem. Ber., 98, 3377 (1965).

(b) 16.6 g. of 1-(2-cyanopropyl)-3-amino-2-pyrazolin- S-one are allowed to react in 80 ml. of pyridine and 160 ml. of benzene and in the presence of 4.5 ml. of phosphorus trichloride with 39 g. of the monosodium salt of a-sulpho-stearic acid, according to the method described in United States patent specification 2,829,975.

The white product obtained does not melt at a temperature lower than 200 C.

PREPARATION 5 1-(.l-methyl-2-cyanoethyl)-3 -pentadecyl-2- pyrazolin-S-one (Formula 12) (a) l-methyl-Z-cyanoethyl hydrazine.To 49 ml. of hydraz ne hydrate, 67 g. of crotononitrile is added dropwise with stirring and keeping the solution at -5 C. The addition occurs at such a rate that all crononitrile is added after 2 hours. Then, the solution is kept for 3 hours at room temperature and evaporated under reduced pressure till completely dry. The oily residue is pure enough to be further used in reaction step (b).

(b) l-(l-methyl-Z-cyanoethyl)-3-pentadecyl 2 -pyrazolin-5-one.9.9 g. of 1-methyl-2-cyanoethyl hydrazine and 31.2 g. of palmitoyl-acetic acid methyl ester are refluxed for 5 min. in 50 ml. of acetic acid. Upon cooling a white precipitate forms which is filtered by suction and recrystallized from methanol. Melting point: 77- 7 8 C.

PREPARATION 6 l-(l-phenyl-Z-cyanoethyl)-3-p-hexadecyloxyphenyl- 2-pyrazolin-5-one (Formula 13) (a) 1-phenyl-2-cyanoethyl hydrazine.This product is prepared according to the method given in preparation 5 (a) starting from hydrazine hydrate and transcinnamonitrile. The product obtained is purified by flash distillation at 120 C./0.01 mm.

(b) l-(l-phenyl 2 cyanoethyl)-3-p-hexadecyloxyphenyl-2-pyrazolin-5-one is prepared by condensation of 1-phenyl-2-cyanoethyl hydrazine with a p-hexadecyloxybenzoyl acetic acid ester analogous to the method of prepartion 2(b).

PREPARATION 7 1- 2,4-dicyanobutyl) -3 -pentadecyl-Z-pyrazolin-S-one (Formula 14) (a) 2,4-dicyanobutyl hydrazine is prepared according. to the method of preparation 5(a) starting from hydrazine hydrate and 2,4-dicyano-butene-1 (dimer of acrylonitrile). The product obtained is purified by flash distillation at 120 C./0.01 mm.

(b) 1 (2,4-dicyanobutyl)-3-pentadecyl-2-pyrazolin-5- one is prepared by cyclisation of 2,4-dicyanobutyl hydra- 6 zine with palmitoylacetic acid methyl ester as described in preparation 5 (b).

The colour couplers for magenta according to the present invention may be of the difi'usible type as well as of the nondilfusible type. By diffusible-type couplers is meant couplers the dispersability or solubility of which is suflicient to enable them to be usefully incorporated in aqueous colour developing baths; an example of such a colour coupler is the colour coupler according to Formula 1. By non-diffusing colour couplers is meant colour couplers of such nature that they are capable of remaining during colour development in the photographic hydrophilic colloid layer(s) in which they have been incorporated.

For manufacturing an appropriate photographic multilayer colour material containing colour couplers for each colour separation image in the differently optically sensitized silver halide emulsion layers, the colour couplers must be present in the hydrophilic silver halide emulsion layers in a non-diifusible form. This object can be accomplished e.g. by the use of a sufliciently water-soluble colour coupler comprising an organic radical which is sufliciently large to prevent the colour coupler from diifusing in the hydrophilic silver halide emulsion layer,

or by the utilization of a lipophilic colour coupler, which. in dissolved state in a high-boiling organic solvent, is dispersed in the silver halide emulsion layer. According to the present invention the said radical rendering the colour coupler non-dilfusible or non migratory is present in the radical R of the above general formula and is preferably an aliphatic radical containing from 5 to 20 carbon atoms in straight line.

For the purpose of incorporating the colour couplers into a photographic colloid layer the couplers can be dissolved either in a low-boiling water-soluble organic solvent or in an appreciably Water-soluble organic solvent and can be finely dispersed in a photographic colloid, e.g.

gelatin. Particularly useful dispersing techniques which can be applied are described in the published Dutch patcut applications 65/ 16423-65/ 1642466/0009866/ 0009 and 66/ 00628.

A particular colour coupler according to the present invention may be incorporated into a silver halide emulsion according to any other appropriate technique known in the art.

In the preparation of a light-sensitive colour material wherein non-migratory colour couplers are used these colour couplers are mixed homogeneously with the lightsensitive silver halide emulsion preferably immediately before the coating of the emulsion.

The couplers according to the above general formula may be used in various kinds of photographic emulsions. They may be added to the emulsions before or after any sensitizing dyes are incorporated. Various silver salts may be used as the sensitive salt, such as silver bromide, silver iodide, silver chloride, or mixed silver halides, such as silver chlorobromide and silver bromoiodide. The colour couplers may be incorporated into emulsions of the mixed packet type such as described in the United States patent specification 2,698,794 or into emulsions of the mixed grain type, such as described in the United States patent specification 2,592,243. The colour couplers can be used in emulsions wherein latent images are formed predominantly on the surface of the silver halide crystal, or in emulsions wherein latent images are formed predominantly inside the silver halide crystal.

The coupler compounds of the present invention may be dispersed in any Water-permeable hydrophilic colloid material, such as gelatin, albumin, casein, zein and the like, and synthetic hydrophilic colloids such as polyvinyl alcohol, that may be used for making photographic emulsions. The emulsions usually also' comprise i.a. spectrally sensitizing agents, hardeners, stabilizing agents and Wetting agents, for facilitating the coating and the adhesion of the emulsion. The thus prepared silver halide emulsion can be coated as one of the layers of a one-layer or multilayer colour material.

The non-migratory colour couplers according to the present invention need not necessarily be provided in the light-sensitive silver halide emulsion layer, but they may also be incorporated into a non-light-sensitive colloid layer adjacent to a silver halide emulsion layer or into a colloid layer in water-permeable relationship therewith.

The non-migratory colour couplers for magenta described in the present invention are added usually, as a solution to a green-sensitized silver halide emulsion. According to a common procedure in the art this silver halide emulsion is coated as the second colour coupler containing layer of a photographic multilayer colour material. Such photographic multilayer colour material usually consists in the given sequence of a support, a red-sensitized silver halide emulsion layer with a colour coupler for cyan, a green-sensitized silver halide emulsion layer with a colour coupler for magenta and a bluesensitive silver halide emulsion layer with a colour coupler for yellow.

A yellow filter layer generally comprising colloidal silver dispersed in gelatin is provided usually between the silver halide emulsion layer containing a colour coupler for yellow and the green-sensitized silver halide emulsion layer.

The colour couplers for magenta according to the present invention may also be applied in so-called droplet emulsions (cf. United States patent specification 2,304,- 940).

Photographic emulsions containing these couplers may be coated on a transparent support such as glass, cellulose esters or on a non-transparent reflecting material, such as paper or an opaque cellulose ester.

For the production of photographic colour images an exposed silver halide emulsion layer is developed preferably With an aromatic primary amine developing substance in the presence of a colour coupler for magenta according to the present invention.

Suitable developing agents are aromatic amine compounds, such as p-phenylene diamine, N,N-dialkyl-pphenylene diamines, such as N,N-diethyl-p-phenylene diamine and derivatives, such as N,N-dialkyl-N'-sulphomethyl p phenylene diamines and N,N-dialkyl-N'-carboxymethyl-p-phenylene diamines.

The dyes formed on colour development show amongst others good fastness to light.

The following examples illustrate the preparation of light-sensitive emulsions and the processing of photographic material according to the present invention.

EXAMPLE 1 To 300 g. of a green-sensitized silver bromoiodide emulsion (2.3 mole percent of iodide), containing per kg. 7.4 g. of dry gelatin and an amount of sliver halide equivalent to 18 g. of silver nitrate, is added a solution of 4.96 g. (0.01 mole) of the colour coupler of Formula 4. This solution is prepared by dissolving the colour coupler at 55 C. in 30 ml. of ethylene glycol monomethyl ether, 7.5 m1, of 2 N sodium hydroxide and 5 ml. of ethanol and then adding ml. of saponin as Wetting agent. The pH of the emulsion is adjusted to pH 6.5 and then the usual additives are incorporated such as hardeners, coating aids, wetting agents and stabilizers. Thereupon the emulsion is diluted with distilled water to 720 ml. and subsequently coated pro rata of 4 g. gelatin/ sq. m. on a cellulose triacetate film support and dried.

After exposure through a grey-wedge the light-sensitive colour material is developed in a developing bath of the following composition:

G. p-N,N-diethylaminophenylammonium chloride 2.75 Sodium sulphite (anhydrous) 2 Potassium carbonate (anhydrous) 75 Potassium bromide 0.50

8 Hydroxylammonium chloride 1.2 Sodium hexametaphosphate (anhydrous) 1.0

Water to 1000 cc.

The developed material is treated for 4 minutes in a stop-bath of the following composition:

Potassium alum g 5 Acetic acid cc 10 Borax g 21 Water up to 1000' cc.

The material is rinsed for 10 minutes with Water and then treated in a fixing bath of the following composition:

G. Sodium thiosulphate-S-water 200 Anhydrous potassium disulphite 25 Potassium alum 15 Boric acid 7.5

Water up to 1000 cc.

After fixing, the material is treated in a bleaching bath of the following composition:

Borax 22 Anhydrous potassium bromide 14 Anhydrous sodium hydrogen sulphite 4 Potassium hexacyanoferrate (III) Water up to 1000 cc.

After ibleaching, the material is rinsed 'With Water for 6 minutes and fixed for another 6 minutes in a bath with the following composition:

G. Anhydrous sodium hexametaphosphate 1 Anhydrous sodium thiosulphate Anhydrous sodium sulphite 10 Anhydrous sodium carbonate 6 Anhydrous sodium hydrogen carbonate 14 Water up to 1000 cc.

After a final rinsing the material is dried. A negative magenta wedge is obtained with an absorption maximum of 542 nm.

EXAMPLE 2 To a same silver halide emulsion as described in Example 1, a solution of 5.98 g. (0.01 mole) of the colour coupler of Formula 6 is added, prepared by dissolving the colour coupler at 55 C. in a mixture of 40 ml. of distilled water, 15 ml. of ethanol and 5 ml. of 2 N sodium hydroxide. The pH of the emulsion is adjusted to pH 6.5 and then the usual additives such as hardeners, wetting agents and stabilizers are added. Thereupon the emulsion is diluted withdistilled Water to 720 ml. and subsequently coated pro rata of 4 g. of gelatin per sq. m. on a cellulose triacetate support and dried.

After exposure through a grey-wedge the material is developed and further treated as in Example 1.

' A negative magenta wedge print is obtained having an absorption maximum of 534 nm.

We claim:

1. A photographic light-sensitive silver halide element containing in a light-sensitive silver halide emulsion layer a non-diffusing Z-pyrazolin-S-one color coupler having the formula:

alkyl group, an aryl group, a heterocyclic group, a NH-aryl group, a NHCO-alkyl group, a -NHCO- aryl group, a NHCO-aralky1 group, a NHCO'NH' alkyl group, a -NHCONH-aryl group, a NHCONH* aralkyl group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, or an aralkyloxycarbonylamino group.

2. The photographic light-sensitive silver halide element of claim 1 wherein the color coupler has the formula (EHz-CHz-CN 3. The photographic light-sensitive silver halide element of claim 1 wherein the color coupler has the formula 10 in the presence of a 2-pyrazo1in-5-one color coupler having the formula:

O=C/ \N Hz( JCR wherein R is hydrogen, an alkyl group or an aryl group and R is hydrogen or an alkyl group, and R represents an alkyl group, an aryl group, a heterocyclic group, a -NH-aryl group, a NHCO-alky1 group, a -NHCO- aryl group, a NHCO-aralkyl group, a NHCONH- alkyl group, a. --NHCONH-aryl group, a NHCONH- aralkyl group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, or an aralkyloxycarbonylamino group.

References Cited US. Cl. X.R. 

